Recent developments in solid-state NMR spectroscopy of crystalline microporous materials

Ashbrook, Sharon E.; Dawson, Daniel M.; Seymour, Valerie R.

doi:10.1039/c4cp00578c

Cited by 77 publications

(92 citation statements)

References 124 publications

(359 reference statements)

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“…Wheatley and Morris observed that, in addition to expected disorder of the protonated and neutral N species of cyclam (owing to the presence of four N atoms and only two H + ), the entire SDA could be refined as occupying two orientations within the pores of AlPO-34(cyclam). 34 In order to investigate the presence of any non-periodic disorder of the SDA and potentially partially-occupied water species, all materials were characterised here by 1 H, 13 C, 15 N, 19 F, 27 Al and 31 P NMR spectroscopy with the experimental results compared to periodic DFT calculations to aid assignment and interpretation.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, as discussed in the Supporting Information (S7), it is difficult to distinguish between the two possible structures using the DFT-calculated 13 The low natural abundance (0.368%) and gyromagnetic ratio (15N/1H = 0.101) of larger chemical shift range (~900 ppm) compared to 13 C (~250 ppm) means that 15 N should be more sensitive to small differences in the local environment of the SDA, arising from, e.g., disorder. The 15 N CP MAS NMR spectra of the six forms of AlPO-34 are shown in Figure 2.…”

Section: Solid-state Nmr Spectroscopymentioning

confidence: 99%

“…12,13 The nature of interactions in the crystalline zeotype product can also be difficult to quantify by, e.g., diffraction methods, which inform only on the average structure and provide little information on motion or local disorder. In this respect, NMR spectroscopy provides an ideal local probe of the solid state [14][15][16] and is particularly suited to the study of zeotypes that contain organic species, since there are several NMR-accessible probe nuclei ( 1 H, 13 C, effects. 22 This is especially powerful when used in combination with crystallographic methods.…”

Section: Introductionmentioning

confidence: 99%

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A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

et al. 2017

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We report a study of the CHA-type aluminophosphate AlPO-34, prepared with six different structure-directing agents (SDAs): piperidine (pip), morpholine (mor), pyridine (pyr), 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,3-dimethylimidazolium (dmim) chloride and 1-ethyl-3-methylimidazolium (emim) bromide. Using a combination of solidstate NMR spectroscopy, periodic density functional theory (DFT) calculations and synchrotron X-ray diffraction, we show that, even in crystallographically well-ordered materials such as AlPO-34 with dmim as the SDA, local disorder may be present. For such disordered structures, where it is challenging to use DFT to assign NMR spectra, we show that the 31 P isotropic chemical shift can be predicted accurately using the mean P-O bond length and P-O-Al bond angle, in an extension of previous work. Variable-temperature 27 Al NMR reveals the presence of microsecond-timescale dynamics in all forms of AlPO-34, with two different motional regimes observed, depending on whether structural H2O is also present. H2O is detected in AlPO-34 prepared with mor as the SDA, although this material was previously reported as anhydrous, suggesting that this form of AlPO-34 may be hygroscopic despite the presence of the SDAs within the pores.

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Section: Resultsmentioning

confidence: 99%

Section: Solid-state Nmr Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

et al. 2017

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“…This is a suitable approach for studying ZIFs, owing to the variety of NMR-active nuclides present [17,18]. 1 H, 13 C and 15 N NMR spectroscopy can, in principle, be used to investigate the number, type and relative proportions of the framework linkers.…”

Section: Introductionmentioning

confidence: 99%

“…NMR spectroscopy has been widely used to investigate the structure of many solids, owing to its sensitivity to the local environment, without the need for any long-range order [15][16][17]. This is a suitable approach for studying ZIFs, owing to the variety of NMR-active nuclides present [17,18].…”

Section: Introductionmentioning

confidence: 99%

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

Sneddon

Kahr

Orsi

et al. 2017

Solid State Nuclear Magnetic Resonance

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Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs) with extended threedimensional networks of transition metal nodes (bridged by rigid imidazolate linkers), with potential applications in gas storage and separation, sensing and controlled delivery of drug molecules. Here, we investigate the use of 13 C and 15 N solid-state NMR spectroscopy to characterise the local structure and disorder in a variety of singleand dual-linker ZIFs. In most cases, a combination of a basic knowledge of chemical shifts typically observed in solution-state NMR spectroscopy and the use of dipolar dephasing NMR experiments to reveal information about quaternary carbon species are combined to enable spectral assignment. Accurate measurement of the anisotropic components of the chemical shift provided additional information to characterise the local environment and the possibility of trying to understand the relationships between NMR parameters and both local and long-range structure. First-principles calculations on some of the simpler, ordered ZIFs were possible, and provided support for the spectral assignments, while comparison of these model systems to more disordered ZIFs aided interpretation of the more complex spectra obtained. It is shown that 13 C and 15 N NMR are sufficiently sensitive to detect small changes in the local environment, e.g., functionalisation of the linker, crystallographic inequivalence and changes to the framework topology, while the relative proportion of each linker present can be obtained by comparing relative intensities of resonances corresponding to chemically-similar species in cross polarisation experiments with short contact times. Therefore, multinuclear NMR spectroscopy, and in particular the measurement of both isotropic and anisotropic parameters, offers a useful tool for the structural study of ordered and, in particular, disordered ZIFs.

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The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

Martineau

Taulèlle

Haouas

2016

Patai's Chemistry of Functional Groups

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Use of 27 Al nuclear magnetic resonance (NMR) spectroscopy for the study of the chemistry of aluminum in a variety of compounds during the last 25 years is reported. A compilation of NMR data, including chemical shifts and heteronuclear scalar couplings, is provided for a wide range of families of aluminum compounds in both solution and solid state. Recent methodological and technological advances in the field of quadrupolar NMR are detailed and their applications to 27 Al nucleus are illustrated. The potential of this technique is exemplified with some representative studies of relevance to mineral, biological, and organic aluminum‐based systems.

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Recent developments in solid-state NMR spectroscopy of crystalline microporous materials

Abstract: This Perspective describes how solid-state NMR spectroscopy can be used to investigate the structure, disorder, dynamics and reactivity of crystalline microporous framework materials.

Cited by 77 publications

References 124 publications

A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

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Recent developments in solid-state NMR spectroscopy of crystalline microporous materials

Abstract: This Perspective describes how solid-state NMR spectroscopy can be used to investigate the structure, disorder, dynamics and reactivity of crystalline microporous framework materials.

Cited by 77 publications

References 124 publications

A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

The Use of27Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

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Product

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The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years